Production of alpha chlorostyrene oxide



States Paggflf ic 2,824,112

P nted. Feb. 18, 1958.

In the above type of epoxy resins the ether linkage is I 2 824 112separated from the carbon atom containing the epoxy i p linkage by atleast one carbon atom. This: arrangement PRODUCTION OF CHLOROSTYRENE maybe illustrated by the general formula William A. McMinn, Jr., Brookline,Mass., assignor to Escambia Chemical Corporation, Pace, Fla a corpoiDelaware In the present invention, there is produced the new compound,alpha chlorostyrene oxide which can be used No Drawing. ApplicationSeptember 24, 1956 to obtain" new and useful types of epoxy resins. Inthese Serial No. 611,769 new resins, the ether linkage in the resin isattached to i one of the carbon atoms containing the epoxy linkage. 5Clams (CL 260 34-8) This arrangement rnay be illustrated by the generalformula i invention relates to the production of chemicals 1!; and m'oreparticularly to the production of alpha chloro styrene oxide; if 1 T Aprincipal object of this invention is to produce the The use of alphachlorostyrene oxide with bisphenol A in niewepmpound, alphachlorostyrene oxide, by thechlori the preparation of an epoxy resinmay'be shown as nation of styrene oxide. f t j o follows:

Other objects of the invention will in part be obvious In one preferredembodiment of the present invention,

and will in part appear hereinafter. alpha chlorostyrene oxide isprepared by a low tempera- The invention accordingly comprises theprocess inture chlorination of styrene oxide. The chlorinationprefvolving the several steps and the relation and the order of erablytakes place at temperatures below about 10 C. one or more of such stepswith respect to each of the and in the presence of a chlorinationcatalyst; the preothers, and the product possessing the features andferred catalyst being ultraviolet light action. In another propertieswhich are exemplified in the following detailed preferred embodiment ofthe invention, the chlorination is disclosure and the scope of theapplication of which carried out in an organic solvent which is inert tochlorine will be indicated in the claims. and the product, alphachlorostyrene oxide. The pref- For a fuller understanding of the natureand objects erable organic solvents are chlorinated hydrocarbons; the ofthe invention, reference should be had to the follow- 0 preferredsolvent being carbon tetrachloride. ing detailed disclosure. A specificdetailed method of practicing the present in- In recent years, thepreparation and use of many epox vention is set forth in the followingnon-limiting examples.

resins has become widely known and has achieved much E l 1 commercialsuccess. One classic example and perhaps xamp e the most widely usedcommercial preparation of epoxy 150 cc. of carbon tetrachloride wereplaced in a flask resins involves the reaction between epichlorohydrinand and cooled to 0 C. grams of styrene oxide were bis-phenol A. Thepreparation of such resins may be then added and the entire contentswere cooled to 5 C. shown as follows: The cooled mixture was thenexposed to ultraviolet light v 3 rays from a suitable source. A veryslight vacuum (about 500 mm.) was maintained on the system throughoutthe reaction to remove hydrogen chloride as rapidly as it was formed.While stirring the mixture, chlorine was then admitted for about 1.5hours, the reaction temperature during this period being controlledbetween about 5 C. and C. Approximately 24.4 grams of chlorine weretaken up by the reaction or enough for a 70 percent conversion ofstyrene oxide to alpha chlorostyrene oxide. The resulting reactionmixture was very fluid and light yellow in color and consisted of about90 grams of product, alpha chlorostyrene oxide.

Example ll About 160 cc. of carbon tetrachloride and 110 grams ofstyrene oxide were placed in a flask and cooled to about C. The cooledmixture was exposed to ultraviolet light rays from a suitable source anda slight vacuum was maintained on the system throughout the reaction.While stirring: the-mixture, chlorine was'admitted for about 1.5 hours,the. reaction temperature during: thisfor complete removal of. hydrogenchloride and/or, chlorine from the final product are within theknowledge of those skilled in the art.

The above reactions proceed as follows:

rt en. cl-o'-- '-cu= The chlorination must be carried out under suchconditions that (1) the epoxy ring is not broken and (2) no substantialamount of polymerization of the styrene oxide takes place. Lowtemperatures and" particularly, temperatures below about 10 C. arepreferable for the reaction. Temperatures above this are conducive topolymerization and breaking of the epoxy ring leading to chlorinatedhydroxy type compounds.

Chlorine, at least in the stoichiometric amount required to form alphachlorostyrene oxide, is employed. However, a slight excess can be used.

The use of an organic solvent, particularly chlorinated hydrocarbonswhich are inert to chlorine and alpha chlorostyrene oxide, is desirablesince it exerts a diluent effect and helps to inhibit or minimizepolymerization of the styrene oxide during the chlorination. Thepreferred solvent has been found to be carbon tetrachloride.

Catalysts may also be employed during the chlorination. In the instantcase, ultraviolet light rays have been found to be suitable as thecatalyst. Other catalysts which can be used in the present reaction arephosphorus trichloride and phosphorus pentachloride.

Since certain changes may be made in the above process and productwithout departing from the scope of the invention herein involved, it isintended that. matter contained in the above description shall beinterpreted as illustrative and not in a limiting sense.

What is claimed is:

1. The process of'prod'ucing" alphachlorostyreneoxide which comprisesreacting at a temperature'below about 10 C. styrene oxide and chlorinein carbon tetrachloride solvent, said reaction mixture being. subjectedto the catalytic efiect of ultraviolet light rays.

2. The new chemical compound, alpha chlorostyrene oxide.

3. The process. for producing alpha. chlorostyrene oxide which.comprises subjecting styrene oxide and ultraviolet light rays at atemperature below about, 1 Q,

4. The process of producing alpha chlorostyreneoxide which comprisessubjecting styrene oxide and chlorijgejm ultraviolet light rays at atemperature below 193 C,

while dissolved in an organic solvent which is inert to chlorine andalpha chlorostyrene oxide.

5. The process of claim 4 wherein said organicsolvent is a chlorinatedhydrocarbon.

No references cited.

1. THE PROCESS FOR PRODUCING ALPHA CHLOROSTYRENE OXIDE WHICH COMPRISESREACTING AT A TEMPERATURE BELOW ABOUT 10*C. STYRENE OXIDE AND CHLORINEIN CARBON TETRACHLORIDE SOLVENT, SAID REACTION MIXTURE BEING SUBJECTEDTO THE CATALYTIC EFFECT OF ULTRAVIOLET LIGHT RAYS.